EP0185482B1 - Elément d'enregistrement d'images pour imprimantes thermiques - Google Patents

Elément d'enregistrement d'images pour imprimantes thermiques Download PDF

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Publication number
EP0185482B1
EP0185482B1 EP85308725A EP85308725A EP0185482B1 EP 0185482 B1 EP0185482 B1 EP 0185482B1 EP 85308725 A EP85308725 A EP 85308725A EP 85308725 A EP85308725 A EP 85308725A EP 0185482 B1 EP0185482 B1 EP 0185482B1
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EP
European Patent Office
Prior art keywords
image
receiving element
element according
wax
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP85308725A
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German (de)
English (en)
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EP0185482A1 (fr
Inventor
Thomas C. C/O Minnesota Mining And Geisler
Terrence A. C/O Minnesota Mining And Black
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3M Co
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Minnesota Mining and Manufacturing Co
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Publication date
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Publication of EP0185482A1 publication Critical patent/EP0185482A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/398—Processes based on the production of stickiness patterns using powders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • This invention relates to image-receiving elements and their use in the formation of images.
  • Thermal print heads can be used to tackify or fluidize the heat-sensitive material to form the latent image.
  • a simple thermal print head comprises at least one resistance element between two conductors.
  • the thermal print head may also comprise an array of resistance elements. Thus, for example, there may be a 5 by 7 element array on the print head. Additionally, the print head may be fixed or moveable with respect to the surface to be imaged.
  • the latent image pattern is formed by contacting the resistance element to the heat-sensitive material, providing electric current to the element for a time sufficient to heat the element and raise its temperature to a level sufficient to melt the material in the area of contact, discontinuing the electric current to the element, and relocating the element with respect to the material.
  • the steps of contacting, heating and relocating are repeated until a sufficient number of melted dot-like areas have been provided to define the desired latent liquid image.
  • the print head has only a single element, the steps necessary to form the latent image must be repeated frequently before an image has been defined.
  • the print head comprises an array (or matrix) of elements, the steps necessary to form the latent image formation need be repeated fewer times.
  • thermal print heads A serious problem frequently encountered with thermal print heads is fouling thereof with the heat-sensitive material of the image receiving surface.
  • the print head is placed in direct contact with the heat-sensitive material. If even a small amount of material from the heat-sensitive coating transfers to the print head and forms a deposit thereon, resolution or image density, or both, is drastically reduced.
  • the thermal print heads are not readily accessible for easy cleaning.
  • Some manufacturers of thermal printers recommend passing coarse bond paper through the printer to abrade the deposits from the print head. It is desirable to increase the interval between recommended cleanings of thermal print heads in order to save time and improve resolution.
  • the image-receiving element of US 3,941,596 comprises a substrate bearing on at least one major surface thereof a coating comprising a) material capable of existing in a supercooled state after melting and subsequent cooling and b) an anti-fouling agent optionally comprising a silica or metal silicate.
  • the present invention provides an image-receiving element as disclosed in US 3,941,596 characterised in that said anti-fouling agent is selected from the group consisting of wax and a mixture of at least one wax and at least one silica or metal silicate.
  • a substrate bearing the aforementioned heat-sensitive coating Upon being imagewise heated with a thermal print head, a substrate bearing the aforementioned heat-sensitive coating becomes tacky in the image areas. Particles of imaging powder can be adhered to these tackified areas. Optionally, the resulting images can be simultaneously or subsequently fixed.
  • the advantage of the heat-sensitive coating described is that the thermal print head will avoid being fouled with residue from the coating material, thus assuring formation of images having high resolution for extended periods of use, without the necessity for frequent cleaning of the print head.
  • the material capable of existing in a supercooled state after melting and subsequent cooling hereinafter referred to as supercooling material, must have a melting temperature about 10°C above ambient temperature.
  • Ambient temperature refers to the temperature of the environment wherein the imaging process is conducted (e.g., at room temperature of about 19°C to 20°C).
  • the material of the coating must also form a supercooled melt when cooled to a temperature below its melting temperature, i.e. these materials exist, at least temporarily, as fluid metastable liquids after being melted and then cooled below their melting temperatures. When the latent image has been formed, it should wet the surface of the substrate.
  • the image must remain fluid and in place until it is contacted with (i.e., developed by) the dry imaging powder. Alternatively, it may be allowed to cool below its melting point to form a supercooled melt before the image areas are developed. Because the supercooled liquid has not regained its solid state, the material retains sufficient memory in the imaged areas to be developed and fixed. Once the material regains its solid state in the imaged areas, the latent image ceases to exist as a distinct area.
  • the supercooling material melts within the approximate range of 40°C to 140°C. Due to the lack in the available chemical literature of adequate data for defining the supercooling materials useful in the practice of the invention, definitive test procedures have been established, one which will now be described.
  • the melting point or melting range of the supercooling material is determined, for the purposes of this invention, by placing a small amount of the material in powder form on a glass microscope slide, covering the sample with a cover glass, heating the material on a microscope having a hot stage which is provided with temperature measuring means, and observing the temperature at which the particles melt and fuse.
  • a test for determining if a material is a supercooling material suitable for this invention is conveniently accomplished using the same sample as for the melting point test.
  • a Leitz hot stage microscope having an electrically heated stage which may be cooled by circulation of cold water is used for both determinations. After the stage has been heated above the melting point of the sample, it is cooled and the temperature noted at which crystallization or solidification occurs. Both heating and cooling may be accomplished at somewhat higher rates of temperature change than are ordinarily specified where more precise measurements are required.
  • a number of supercooling materials are useful in the coatings of the invention. Representative examples of these materials include dicyclohexyl phthalate, diphenyl phthalate, triphenyl phosphate, dimethyl fumurate, benzotriazole, 2,4 - dihydroxy benzophenone, tribenzylamine, benzil, vanillin, and phthalophenone. Another useful material of this type is "Santicizer 9", a mixture of ortho- and para-toluene sulfonamides commercially available from the Monsanto Chemical Company. Mixtures of these materials are also useful.
  • the supercooling material can also consist of two or more materials that are not supercooling by themselves, but are combinable to form a supercooling material.
  • the anti-fouling agent can be selected from the following classes of materials:
  • anti-fouling agent means a material, i.e., a chemical compound or mixture of chemical compounds, that is added to the heat-sensitive composition that inhibits or prevents foreign substances from being deposited on the thermal print head.
  • the materials that are useful as anti-fouling agents in the composition of this invention have at times been referred to as lubricants and antiblocking agents.
  • Waxes that are suitable for the composition of the present invention include aliphatic alcohols having at least 10 carbon atoms, fatty acids having at least 12 carbon atoms, fatty amides having at least 12 carbon atoms, fatty acid esters having at least 12 carbon atoms, symmetrical ketones derived from fatty acids having at least 12 carbon atoms, metal salts of fatty acids having at least 12 carbon atoms, and fluorocarbon polymers.
  • Fatty amides that are suitable for the compositions of this invention can be represented by the formula wherein
  • fatty amides include stearamide, lauramide, oleamide, ethylene - bis - stearamide and mixtures thereof.
  • Fatty acid esters that are suitable for the compositions of this invention can be represented by the formula wherein
  • Suitable fatty acid esters include glyceryl stearates, e.g. glyceryl monostearate and diethylene glycol monostearate, glycol stearates, cetyl palmitate, stearyl stearate, n-butyl stearate, n-octyl stearate.
  • Symmetrical ketones that are suitable for the composition of this invention can be represented by the formula wherein
  • symmetrical ketones derived from fatty acids that are useful in compositions of this invention inlcude stearone and laurone.
  • Metal salts of fatty acids that are suitable for the compositions of this invention can be represented by the formula wherein
  • Metal salts of fatty acids that are suitable for the composition of the present invention include octoates, laurates, palmitates, and stearates of aluminum, lead, cadmium, barium, calcium, lithium, magnesium, and zinc.
  • the metal stearates are most preferred.
  • Blends of metal salts of fatty acids, e.g. zinc stearate, and fatty acids, e.g. stearic acid, are also useful as anti-fouling agents in the composition of the present invention.
  • One or more of the hydrogen atoms of the hydrocarbon radicals R 1 , R 2 , R 3 can be replaced with other atoms, e.g., halide, or groups of atoms, e.g. hydroxyl, so long as said atoms or groups of atoms do not adversely affect the anti-fouling characteristics of the wax anti-fouling agent.
  • Fluorocarbon polymers that are suitable for the composition of the present invention include polymeric tetrafluoroethylene.
  • Silicas and metal silicates can be used as components of the anti-fouling agent in the composition of the present invention.
  • Representative examples of these materials include silica gel, fumed silica, precipitated silica, clay, kaolin, and talc.
  • the silicas and metal silicates can be blended with waxes such as for example metal salts of fatty acids, e.g. metal stearates, fluorocarbon polymers, e.g., polytetrafluoroethylene, and fatty amides, e.g. stearamide, which improves their anti-fouling action.
  • waxes such as for example metal salts of fatty acids, e.g. metal stearates, fluorocarbon polymers, e.g., polytetrafluoroethylene, and fatty amides, e.g. stearamide, which improves their anti-fouling action.
  • Binders are desirably included in the heat-sensitive composition of the image receiving element.
  • the heat-sensitive composition would tend to flake off under certain conditions in the absence of binders.
  • Representative examples of organic polymeric binders suitable for this invention include water soluble binders such as polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, and organic solvent soluble binders such as cellulose acetate, ethyl cellulose, and polyvinyl chloride.
  • Substrates suitable for use in the invention can be selected from any dry, solid material that is compatible with the coating of normally solid, non-tacky material.
  • materials suitable for the substrate include polymeric films, metal foils, and paper.
  • the preferred substrate is paper.
  • the range of concentration of each ingredient in the heat-sensitive coating material has been found to be important. If too little anti-fouling agent is employed, the thermal print heads will become fouled relatively rapidly. If too much anti-fouling agent is employed, the optical density of the toned image will be too low.
  • concentration ranges for essential ingredients of the heat-sensitive coating material are as follows:
  • the concentration ranges for essential ingredients of the heat-sensitive material are as follows:
  • the coating material can be applied to the surface of a substrate by a variety of techniques, including both solvent coating and dry coating.
  • the heat-sensitive coating material can be dissolved or dispersed in an appropriate solvent (e.g., acetone, or water), the solution or dispersion applied to the substrate, and the solvent allowed to evaporate.
  • the previously dissolved or dispersed solid material is then allowed to crystallize. Evaporation of the solvent can be accelerated, if desired, by heating the coated substrate.
  • crystallization of the dissolved or dispersed solid material can be accelerated by seeding the coated substrate with like solid material.
  • Dry coating techniques can also be utilized.
  • the solid form of the heat-sensitive coating material can be brushed or rubbed onto the substrate.
  • the solid form of the material is either in the form of a powder or in a form in which it can readily be converted to a powder.
  • the dry coating technique is an efficient means for applying the material to the substrate. Materials applied by the dry coating technique do not soak into the substrate as they do with solvent coating techniques. This is beneficial since it reduces the amount of coating material applied to the substrate while continuing to provide as good an image as that when the coating material is applied by a solvent coating technique.
  • the resultant sheet appears indistinguishable from an uncoated paper sheet and can be used immediately after coating.
  • the exact amount of the coating material on the substrate can vary. There should be sufficient coating material to form a latent image but not so much material that the thermal printing means is adversely affected, the article becomes too dielectric, or gives a greasy feel or appearance. A sufficient amount of coating material must be used so that once the latent image has been formed, there will be sufficient adhesion between it and the imaging powder to overcome the triboelectric or magnetic forces, or both, holding the imaging powder to the development roll.
  • the substrate preferably bears from 0.1 to 2 g/m 2 of the material, more preferably from about 0.1 to 1.2 g/m 2 , and most preferably from about 0.2 to 1.0 g/m 2 of the material. These relatively small amounts of coating material are sufficient to provide latent images that can be developed and essentially permanently fixed to the substrate.
  • the particulate material is substantially absorbed onto the substrate surface.
  • the substrate is paper
  • the material becomes attached to the surface of the paper fibers.
  • the imaged area must provide sufficient adhesion to the dry imaging powder.
  • the imaged area may react with the imaging powder; it may form a solution with the powder; it may wet the powder; or it may either absorb or be adsorbed by the powder. Whatever the interaction between the powder and the imaged area is, the imaged area must hold the powder until the powder is fixed to the substrate.
  • Coatings were evaluated by printing a solid bar (0.66 m (26 inches) long) with the thermal print head in the EMT 9140 Facsimile Machine (3M Company). The latent image was then developed with the toner station of a VQC compact copier (3M Company) and toner powder described in U.S. Patent No. 3,925,219, Example 1. The toner particles ranged in size from 10 to 45 micrometers.
  • the printer utilized a 3.94 styli/mm (100 styli/inch) thick film print head manufactured by Rolm Corporation.
  • Print head residue was evaluated by visually inspecting the head under 5x magnification and rated according to the following criteria:
  • Image density after development was measured with a MacBeth TR 924 densitometer in reflection mode.
  • Coating material formulations are set forth in Table I. In the following table the amounts are in parts by weight.
  • the phthalates and cellulosic binders were dissolved in acetone.
  • the wax anti-fouling agents were dispersed into the phthalate/binder/acetone solution using an ultrasonic bath.
  • the filler anti-fouling agents were dispersed into the phthalate/binder/acetone solution using a homogenizer.
  • the dispersions were coated on paper with a 13 mm (1/2 inch) diameter #8 wire wound rod and air dried, yielding a dry coat weight of 3.01 to 3.88 g/mm 2 (0.28 to 0.36 g/ft 2 ).
  • print head residue ranged from light to heavy.
  • print head residue ranged from none to trace.
  • This example demonstrates the effect of coating weight on printhead residue.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (21)

1. Elément d'enregistrement d'images comprenant un substrat portant au moins sur une de ses surfaces principales un revêtement comprenant a) une matière capable d'exister à l'état surfondu après fusion puis refroidissement et b) un agent anti-encrassement comprenant facultativement une silice ou un silicate métallique, caractérisé en ce que ledit agent anti-encrassement est choisi parmi l'ensemble constitué par une cire et un mélange d'au moins une cire et d'au moins une silice ou un silicate métallique.
2. Elément d'enregistrement d'images selon la revendication 1 comprenant de plus un liant.
3. Elément d'enregistrement d'images selon la revendication 1 ou la revendication 2, dans lequel ledit agent anti-encrassement est constitué d'une cire.
4. Elément d'enregistrement d'images selon l'une quelconque des revendications précédentes, dans lequel ladite cire est choisie parmi l'ensemble constitué par les alcools aliphatiques, les acides gras, les amides gras, les esters d'acide gras et les cétones symétriques dérivées d'acides gras.
5. Elément d'enregistrement d'images selon la revendication 4, dans lequel ladite cire est représentée par la formule
Figure imgb0030
dans laquelle R1 représente un radical hydrocarboné saturé ou insaturé ayant de 9 à 21 atomes de carbone.
6. Elément d'enregistrement d'images selon la revendication 4, dans lequel ladite cire est représentée par la formule
Figure imgb0031
dans laquelle R2 représente un radical hydrocarboné saturé ou insaturé ayant de 11 à 21 atomes de carbone.
7. Elément d'enregistrement d'images selon la revendication 4, dans lequel ladite cire est représentée par la formule
Figure imgb0032
dans laquelle R2 représente un radical hydrocarboné saturé ou insaturé ayant de 11 à 21 atomes de carbone, et
X représente
Figure imgb0033
ou H.
8. Elément d'enregistrement d'images selon la revendication 4, dans lequel ladite cire est représentée par la formule
Figure imgb0034
dans laquelle
R2 représente un radical hydrocarboné saturé ou insaturé ayant de 11 à 21 atomes de carbone, et
R3 représente un radical hydrocarboné ayant de 1 à 21 atomes de carbone.
9. Elément d'enregistrement d'images selon la revendication 4, dans lequel ledit agent anti-encrassement est représenté par la formule
Figure imgb0035
dans laquelle R2 représente un radical hydrocarboné saturé ou insaturé ayant de 11 à 21 atomes de carbone.
10. Elément d'enregistrement d'images selon l'une quelconque des revendications 1 à 3, dans lequel ladite cire est un sel métallique d'un acide gras.
11. Elément d'enregistrement d'images selon la revendication 10, dans lequel ladite cire est représentée par la formule
Figure imgb0036
dans laquelle
R2 représente un radical hydrocarboné saturé ou insaturé ayant de 11 à 21 atomes de carbone,
n est un entier valant de 1 à 3 inclusivement, et
M représente un atome métallique.
12. Elément d'enregistrement d'images selon l'une quelconque des revendications 1 à 3, dans lequel ladite cire est une cire fluorochimique.
13. Elément d'enregistrement d'images selon l'une quelconque des revendications 3 à 12, dans la mesure où elles sont dépendantes de la revendication 2, dans lequel ladite matière capable d'exister à l'état surfondu après fusion, puis refroidissement, constitue 55% à 99% du poids du revêtement, ladite cire constitue 1 % à 16% du poids du revêtement et ledit liant constitue jusqu'à 40% du poids du revêtement.
14. Elément d'enregistrement d'images selon l'une quelconque des revendications 4 à 13, dans la mesure où elles dépendent de la revendication 1 ou de la revendication 2, dans lequel ledit agent anti-encrassement est constitué d'un mélange d'une cire et soit d'une silice, soit d'un silicate métallique.
15. Elément d'enregistrement d'images selon la revendication 14, dans lequel ladite matière capable d'exister à l'état surfondu après fusion, puis refroidissement, constitue 50% à 95% du poids du revêtement, ledit agent anti-encrassement constitue 5% à 40% du poids du revêtement et ledit liant constitue 3% à 40% du poids du revêtement.
16. Elément d'enregistrement d'images selon l'une quelconque des revendications précédentes, dans lequel ladite matière capable d'exister à l'état surfondu peut être surfondue à une température inférieure d'au moins 60°C à son point de fusion.
17. Elément d'enregistrement d'images selon l'une quelconque des revendications précédentes, dans lequel ledit substrat est un papier, une pellicule polymère ou une pellicule métallique.
18. Procédé pour préparer une image comprenant les stades consistant à:
1) faire appel à un élément d'enregistrement d'images selon l'une quelconque des revendications précédentes,
2) chauffer des régions choisies dudit élément d'enregistrement d'images avec une tête d'impression thermique pour porter lesdites régions choisies dudit revêtement dans un état où elles peuvent adhérer à une poudre formatrice d'images,
3) appliquer une poudre formatrice d'images auxdites régions choisies pour former une image développée sur ledit élément d'enregistrement d'images.
EP85308725A 1984-12-10 1985-11-29 Elément d'enregistrement d'images pour imprimantes thermiques Expired - Lifetime EP0185482B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67981984A 1984-12-10 1984-12-10
US679819 2003-10-06

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EP0185482A1 EP0185482A1 (fr) 1986-06-25
EP0185482B1 true EP0185482B1 (fr) 1990-04-11

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EP (1) EP0185482B1 (fr)
JP (1) JPS61143194A (fr)
KR (1) KR940007771B1 (fr)
BR (1) BR8506114A (fr)
CA (1) CA1248351A (fr)
DE (1) DE3577064D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4608329A (en) * 1985-01-08 1986-08-26 Minnesota Mining And Manufacturing Company Imageable toner powder
JPS6295290A (ja) * 1985-10-23 1987-05-01 Seiko Epson Corp 印写装置
JPS6321185A (ja) * 1986-07-15 1988-01-28 Mishima Seishi Kk 熱転写プリンタ−用記録用紙
US4871715A (en) * 1988-07-01 1989-10-03 Eastman Kodak Co. Phthalate esters in receiving layer for improved dye density transfer
US5478614A (en) * 1994-10-07 1995-12-26 Minnesota Mining And Manufacturing Company Infrared sensitive recording medium with fluorocarbon surfactant

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941596A (en) * 1962-10-24 1976-03-02 E. I. Du Pont De Nemours And Company Thermographic processes using polymer layer capable of existing in metastable state
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4181771A (en) * 1977-11-04 1980-01-01 Ncr Corporation Thermally responsive record material
JPS5491338A (en) * 1977-12-28 1979-07-19 Jujo Paper Co Ltd Thermosensitive recording paper

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BR8506114A (pt) 1986-08-26
DE3577064D1 (de) 1990-05-17
JPS61143194A (ja) 1986-06-30
KR860005255A (ko) 1986-07-21
EP0185482A1 (fr) 1986-06-25
KR940007771B1 (ko) 1994-08-25
CA1248351A (fr) 1989-01-10

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